Process for dyeing with reactive dyes in



United States Patent 3,097,041 PROCESS FOR DYEING WITH REACTIVE DYES [NWATER-SOLUBLE THIOL COMPOUND Gordon Hobson Lister, 152 Canal Road,Bradford 2, England, and Hermann Egli, 47 Aralienstrasse, Basel,

Switzerland No Drawing. Filed June 27, 1960, Ser. No. 38,761

Claims priority, application Switzerland June 26, 1959 Claims. (11.s--s4 wherein R represents a divalent hydrocarbon radical.

The Compound I can he of araliphatic, cycloaliphatic, or preferably ofaromatic or aliphatic nature, e.g. thioglycolic acid, aorB-mercaptopropionic acid, mercaptobutyric acid, mercaptoisobutyric acid,a-mercaptovaleric acid, mercaptosuccinic acid, or 3- or4-mercaptobenz0ic acid. It is employed as the free acid or in the formof one of its water-soluble salts, e.g. an earth alkali metal, alkalimetal, ammonium or amino salt.

The compound of Formula I is advantageously employed in amounts of 1% to20% by weight of the goods in the dyebath itself. The bath in which itis used must also contain an inorganic or organic acid, e.g. sulphuric,phosphoric, acetic or formic acid, or the ammonium salt of such an acid.Esters, e.g. glycol diacetate, are also suitable as acid donors. At theend of the dyeing proc ess the pH value of the dyebath is adjusted to7-7.5 by the addition of an alkali or an alkali donor, e.g. ammonia,urotropine, or a builer mixture, and the dyeing is after treated in thebath with heating and, if desired in presence of ions of a heavy metalsuch as chromium, nickel, manganese, cobalt, iron or copper.

The reactive dyestuffs suitable for the process are those containing atleast one reactive group which possesses at least one su'bstituent whichcan be easily split ed as an anion.

The preferred reactive group of this type is the radical of an acidcontaining at least one mobile halogen atom, e.g. chloroacetic acid,bromoacetic acid, fi-chloroor [S- bromopropionic acid, a-chloro-,p-chloro, a-br0m0- or fi-bromoacrylic acid, 12-, or Bfi-dichloroordibromoacrylic acid, trichloroor tribromoacrylic acid, (1-, 5-, 'ychlorocrotonic acid, 11-, 13-, y-bromocrotonic acid,anti-dichlorocrotonic acid, monochloroor monobromomaleic acid,dichloroor dibromomaleic acid, monochloroor monobromofumaric acid,dichloroor dibromofumaric acid, dichloro-or dibromofumaric acid,dichloroor dibromosuccinic acid, or the radical of one of the followingheterocyclic compounds: cyanuric chloride, cyanuric bromide, primarycondensation products of the cyanuric chloride of the composition:

wherein represents the radical, which may contain further suhstituents,or a primary or secondary aliphatic, alicyclic, aromatic or heterocyclicamine, an aliphatic, alicyclic, aromatic or heterocyclic hydroxy orthiol compound, in particular the radical of aniline its alkyl, sulicefonic acid or carboxylic acid derivatives, or of a low molecular monoordial'kyl amine or ammonia, 2,4,6-trichloropyrimidine,2,4,6-tribromopyrimidine and their derivatives which may contain thefollowing suhstituents in the 5-postion: methyl, ethyl, carboxylic acidor sulfonic acid amide which may be substituted on the nitrogen atom,carboxylic acid methyl or ethyl ester, acyl, e.g. acetyl, benzoyl,alkylene, e.g. allyl, substituted alkyl, e.g. 2-ketopropyl,carboxymethyl, chloroor bromomethyl, a methylene group between twopyrimidine nuclei, 2,4,5,6- tetrachloroor tetrabromopyrimidine,2,6-dichloroor -dibromopyrimidine-4-carboxylic acid ethyl ester, 2,4,5-trichloro-pyrimidine, 4- or S-carboxylic acid amide or sulfonic acidamide derivatives of 2,6-dichloroor -dibromopyrimidine which may hesubstituted on the nitrogen atom, 2,5,6-trichloro-4-methylpyrimidine or2,6-dichloro-4-trichloromethylpyrimidine.

The dyeings obtained possess excellent wet fastness properties (water,washing, milling, perspiration and rubhing fastness) and very goodstability to dry cleaning. Acetate, triacetate or polyethyleneterephthalate fibers which are present in the dyebath are reserved.

In the following examples the parts and percentages are by weight andthe temperatures in degrees centigrade.

Example 1 100 parts of wool in hank form are placed in a dyeing machinewith circulating liquor flow. 2000 parts of water, 2 parts of aceticacid, 0.5 part of the condensation product of 1 mole of oleylamine and 8moles of ethylene oxide, and 5 parts of ammonium thioglyoolate areadded. The dyebath is rapidly heated to 50 and maintained at thistemperature for 5 minutes. After the addition of 2 parts of the reactivedyestufl, produced by condensation of 1 mol of 2,4,6 trichloropyrimidinewith 1 mole of l-hydroxy-Z-phenylazo-S-aminonaphthalene-Z,3,6-trisulfonic acid, the temperature is raised to 98 in 30 minutes andthis temperature maintained for 1 hour, The dyebath is then neutralizedby the addition of 5 parts of hexamethylene tetramine and boiled for afurther 20 minutes. The dyed goods are subsequently rinsed and dried.The red dyeing thus produced possesses very good wet fastnessproperties.

Equally good results are obtained when the abovementioned dye-stud isreplaced by one of the following dyestuffs: the condensation product of1 mole of 2,4,6- trichloropyrimidine and 1 mole of1-hydroxy-2-(4-methyl)-phenylazo-8-aminonaphthalene-2',3,6-trisulfonicacid or 1 mole of 1-(2',5dichloro)-phen.yl-3-methyl-4-(3"-amino)-phenylazo-5-pyrazolone-4',6" disulf0nic acid or the condensationproduct of 1 mole of tetrachloropyrimidine and 1 mole of copperphthalocyanine sulfonic acid- (3'-arnino)-phenylamide-trisulfonic acid,or 1 mole of lamino-4- 3 -amino) phenylaminoanthraquinone 2,4-disulfonicacid or 1 mole of l-amino-4-(2',4',6'-trimethyl- 3'-amino) phenylaminoanthraquinone 2,6-disulfonic acid.

Ammonium thioglyoolate can be replaced by an equivalent amount of aorfi-mercaptopropionio acid, mercaptobutyric acid,mercapto-isobutyric-4-mercaptobenzoic acid or their ammonium salts.

Example 2 100 parts of scoured loose wool are introduced into a dyebathof 2000 parts of water, 2 parts of 80% acetic acid, 1 part of cetyleicosaglycol ether, 0.3 part of N- sitearoylaminopropyl-N,N-di-(n-hutyl)N benzylamrmonium chloride, 10 parts of ammonium thioglyoolate, and 2parts of the reactive dyestulf produced by condensation of 1 mole of2,4,6-trichloropyrimidine with 1 mole of 1- hydroxy-2-(4'-methyl)phenylazo 8 aminonaphthalene- 2,3,6-trisulfonic acid. From the startingtemperature of 50 the dyebath is raised to 98 in 30 minutes and boilingcontinued for 30 minutes. 0.2 part of manganese chloride are added andthe bath boiled for a further 30 minutes. Its pH is then adjusted for7.5 with the addition of ammonia, and boiling is continued for a further30 minutes. A red dyeing of high wet fastness is obtained.

Example 3 100 parts of scoured loose wool are entered into a dyebath of2000 parts of water containing 4 parts of thioglycolic acid, 1 part ofcetylpyridinium bromide and 2 parts of the reactive dyestufi produced bycondensation of 1 mole of 2aphenylamino-4,6-dichloro-l,3,5-triazine-4-sulfonic acid with 1 mole of 1-amino-4-(3-amino)-phenylaminoanthraquinone-2,4'-disulfonic acid.

From its initial temperature, 50, the dyebath is raised to 98 in 30minutes and dyeing is continued for 1 hour at this temperature. The pHvalue is then brought to 7.5 by the addition of sodium carbonate, 2parts of chromium fluoride are added and the dyebath maintained at 100for a further 30 minutes. A brilliant blue dyeing of high wet fastnessis obtained.

Equally good results are obtained when the abovementioned dyestutf isreplaced by one of the following: the condensation product of 1 mole of2-phenylamino-4, 6-dioh1oro'1,3,5-tniazine-3- or -4'-sulfonic acid and 1mole ofl-hydroxy-2-(4'-methyl)-phenylazo-8-aminonaphthalene-2',3,6-trisulfonicacid or 1 mole of 1-(2,5-dichloro) phenyl-3 methyl-4 (3"-amino)phenylazo-S- pyrazolone-4',6"-disulfonic acid or the condensationprodnot of 1 mole of2-phenylamino4,6-dichloro-1,3,5-triazine-3'-sulfonic acid and 1 mole ofcopper phthalocyaninesu'ltonic acid (3'amino) phenylamide-trisulfonicacid, or 1 mole of1-amino-4-(4'-amir1o)-phenylaminoantl1raquin7one-2,3'-disulfonic acid or1 mole of l-amino- 4 (2,4',6'-trimethyl-3'-amino)phenylaminoanthraquinone-2,6-disulfonic acid.

Having thus disclosed the invention what We claim is: 1. A process fordyeing keratin-containing fibers with reactive dyestufls, which consistsin (l) treating the fibers in aqueous acid medium at a temperature ofmaximally C. with a reducing compound of the formula wherein R isdivalent hydrocarbon radical of 1 to 6 carbons, whereby the cystinebridge of keratin is split into SH groups, and

(2) concurrently treating the fibers with a reactive dye selected fromthe group consisting of 2.20, anthraquinone and phthalocyanine dyesbearing one to two halogen atoms of an atomic weight between 35 and 81.

2. The process of claim 1 in which thioglyoolic acid is the reducingcompound.

3. The process of claim 1 in which mercaptopropionic acid is thereducing compound.

4. The process of claim 1 in which mercaptobutyric acid is the reducingcompound.

5. The process of claim 1 in which mercaptosuccinic acid is the reducingcompound.

6. The process of claim 1 in which B-mercaptobenzoic acid is thereducing compound.

7. The process of claim 1 in which 4-mercaptobenzoic acid is thereducing compound.

References Cited in the file of this patent UNITED STATES PATENTS2,739,033 Lubs Mar. 20, 1956 2,876,781 Martin Mar. 10, 1959 2,933,365Moore Apr. 19, 1960 2,975,167 Schwander a a]. May 14, 1961

1. A PROCESS FOR DYEING KERATIN-CONTAINING FIBERS WITH REACTIVEDYESTUFFS, WHICH CONSISTS IN (1) TREATING THE FIBERS IN AQUEOUS ACIDMEDIUM AT A TEMPERATURE OF MAXIMALLY 100*C. WITH A REDUCING COMPOUND OFTHE FORMULA